Method of manufacturing semiconductor device, semiconductor device and substrate processing apparatus

ABSTRACT

An oxide film capable of suppressing reflection of a lens is formed under a low temperature. A method of manufacturing a semiconductor device includes forming a metal-containing oxide film on a substrate by performing a cycle a predetermined number of times, the cycle comprising: (a) supplying a metal-containing source to the substrate; (b) supplying an oxidizing source to the substrate; and (c) supplying a catalyst to the substrate.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This application is a continuous application of U.S. patent applicationSer. No. 14/248,961 filed on Apr. 9, 2014, which is a continuation ofU.S. patent application Ser. No. 13/293,636 filed on Nov. 10, 2011,which issued as U.S. Pat. No. 8,847,343 on Sep. 30, 2014, which claimspriority under 35 U.S.C. §119 to Japanese Patent Applications No.2010-261571 filed on Nov. 24, 2010 in the Japanese Patent Office, andthe entire contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of manufacturing asemiconductor device, a semiconductor device, and a substrate processingapparatus.

2. Description of the Related Art

A micro lens configured to collect light for a light receiving elementinstalled on, for example, a semiconductor device, has been used insemiconductor devices such as complementary metal oxide semiconductor(CMOS) image sensors. As the CMOS image sensor is highly integrated,light-collecting efficiency of the lens has been promoted to receivemore sufficient incident light through the micro lens.

PRIOR ART DOCUMENTS Patent Documents

1. Japanese Patent Laid-open Publication No.: 2009-177079

2. U.S. Pat. No.: 6,534,395

SUMMARY OF THE INVENTION

In order to improve light-collecting efficiency of a lens, for example,reflection of incident light from a surface of the lens may besuppressed. Since the reflection is more likely to occur as a differencein refractive index between media through which light passes, i.e., air(a low refractive index) and a lens (a high refractive index),increases, the reflection can be suppressed by forming a film of amaterial having a refractive index therebetween, for example, an oxidefilm, on the lens to attenuate the difference in refractive index. Suchan oxide film has been formed on, for example, a lens formed on asubstrate, using a source including a predetermined element and anoxidizing agent.

However, since the refractive index is fixedly determined by a kind ofthe oxide film and the difference in refractive index between the mediais insufficiently attenuated by only installing the oxide film having apredetermined refractive index on the lens, the reflection may beinsufficiently suppressed. That is, when an oxide film having a lowrefractive index closer to the air is selected, reflection at aninterface with the lens cannot be easily suppressed, and when an oxidefilm having a high refractive index closer to the lens is selected,reflection at an interface with the air cannot be easily suppressed. Inaddition, when the lens is formed of, for example, a resin material,since a substantial reactivity between the source and the oxidizingagent cannot be obtained under a low temperature at which no thermaldenaturation occurs from the resin material, the oxide film cannot beeasily formed.

Therefore, an object of the present invention is to form an oxide filmcapable of suppressing reflection of a lens under a low temperature.

According to an aspect of the present invention, there is provided amethod of manufacturing a semiconductor device, including forming ametal-containing oxide film on a substrate by performing a cycle apredetermined number of times, the cycle including: (a) supplying ametal-containing source to the substrate; (b) supplying an oxidizingsource to the substrate; and (c) supplying a catalyst to the substrate.

According to another aspect of the present invention, there is provideda method of manufacturing a semiconductor device, including forming alaminated film wherein a silicon-containing oxide film and ametal-containing oxide film are alternately stacked on a substrate byalternately performing, a predetermined number of times, (a) performinga first cycle a predetermined number of times, the first cycleincluding: supplying a silicon-containing source to the substrate;supplying an oxidizing source to the substrate; and supplying a catalystto the substrate to form the silicon-containing oxide film; and (b)performing a second cycle a predetermined number of times, the secondcycle including: supplying a metal-containing source to the substrate;supplying an oxidizing source to the substrate; and supplying a catalystto the substrate to form the metal-containing oxide film.

According to still another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) forming a laminated film wherein a silicon-containing oxide film anda metal-containing oxide film are alternately stacked on a substrate byalternately performing, a predetermined number of times, (a-1)performing a first cycle a predetermined number of times, the firstcycle including: supplying a silicon-containing source to the substrate;supplying an oxidizing source to the substrate; and supplying a catalystto the substrate to form the silicon-containing oxide film; and (a-2)performing a second cycle a predetermined number of times, the secondcycle including: supplying a metal-containing source to the substrate;supplying an oxidizing source to the substrate; and supplying a catalystto the substrate to form the metal-containing oxide film; and (b)forming a silicon-containing oxide film on the laminated film byperforming a third cycle a predetermined number of times, the thirdcycle including: supplying a silicon-containing source to the substrate;supplying an oxidizing source to the substrate; and supplying a catalystto the substrate.

According to a method of manufacturing a semiconductor device, asemiconductor device and a substrate processing apparatus of the presentinvention, an oxide film capable of suppressing reflection of a lens canbe formed under a low temperature.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a substrate processing apparatus inaccordance with a first embodiment of the present invention;

FIG. 2 is a view of a process furnace in accordance with the firstembodiment of the present invention, particularly showing across-sectional view of a process chamber;

FIG. 3 is a view of the process furnace in accordance with the firstembodiment of the present invention, particularly showing across-sectional view taken along line A-A of the process chamber of FIG.2;

FIG. 4 is a flowchart illustrating a substrate processing process inaccordance with the first embodiment of the present invention;

FIG. 5 is a gas supply timing chart of the substrate processing processin accordance with the first embodiment of the present invention;

FIGS. 6A and 6B are views for explaining a catalyst reaction of thesubstrate processing process in accordance with the first embodiment ofthe present invention;

FIG. 7 is a flowchart illustrating a substrate processing process inaccordance with a second embodiment of the present invention;

FIG. 8 is a gas supply timing chart of the substrate processing processin accordance with the second embodiment of the present invention;

FIGS. 9A and 9B are views for explaining a catalyst reaction of thesubstrate processing process in accordance with the second embodiment ofthe present invention;

FIGS. 10A and 10B are schematic views showing a refractive index of alens installed on a semiconductor device in accordance with a referenceexample and the first embodiment; and

FIGS. 11A and 11B are schematic views showing a refractive index of alens installed on a semiconductor device in accordance with a relatedart example and the reference example.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

<Inventors' Comments>

First, before describing embodiments of the present invention, somecomments from the inventors will be explained.

As described above, a semiconductor device such as a CMOS image sensoris manufactured by forming a light receiving element configured toconvert light into an electrical signal, an interconnection configuredto process the electrical signal, and so on, on a substrate. Forexample, a small lens (a micro lens) is installed over the lightreceiving element to collect light for the light receiving device.

In a conventional semiconductor device shown in FIG. 11A, incident light5 which arrives at a resist lens 10, which is a lens formed of photoresist, partially arrives at a photo diode 30, which is a lightreceiving element (a refractive light 7 a), and is partially reflected(a reflective light 6 a). Since a difference in refractive index betweenthe air (refractive index: 1.0) and the resist lens 10 (refractiveindex: 1.6), through which light passes, is large, reflection can easilyoccur. For this reason, in the conventional semiconductor device,light-collecting efficiency of the resist lens 10 becomes insufficient,and thus, only a weak electrical signal having a large noise ratio maybe obtained.

On a semiconductor device according to a reference example shown in FIG.11B, for example, a SiO film 20 is formed on a resist lens 10 as onemethod of suppressing reflection. The difference in refractive index isattenuated by the SiO film 20 (refractive index: 1.45) having arefractive index between the air and the resist lens 10 to somewhatsuppress the reflection (reflective light 6 a and 6 b) on each filmsurface.

However, since the refractive index of the oxide film is fixedlydetermined by a kind of the oxide film such as the SiO film 20, thereflection cannot be substantially suppressed by a predetermined oxidefilm only. While the refractive index is adjusted by appropriatelyselecting the kind of the oxide film to suppress the reflection at thefilm surface, when the oxide film having a refractive index closer tothe air is formed, the reflection at a surface of the resist lens 10cannot be easily suppressed, and when the oxide film having a refractiveindex closer to the resist lens 10 is formed, the reflection at aninterface with the air cannot be easily suppressed.

In addition, in the semiconductor device according to the referenceexample, there have been problems involving a temperature upon filmforming. The oxide film is formed on the lens of the substrate bysupplying a source and an oxidizing source into a process chamber inwhich the substrate is accommodated and reacting the source and theoxidizing source. However, as described above, when the lens is formedof a resin material such as photo resist, under a temperature at whichno thermal denaturation occurs from the resin material, for example, alow temperature equal to or lower than 200° C., reaction between thesource and the oxidizing source cannot be sufficiently generated and theoxide film cannot be easily formed.

Therefrom, the inventors have performed research on means for solvingthese problems. As a result, it has been ascertained that, when an oxidefilm is formed, reflection can be suppressed by varying a refractiveindex of the oxide film in a thickness direction. In addition, it hasbeen ascertained that the oxide film can be formed even under a lowtemperature by supplying catalyst or using plasma. The present inventionis based on these discoveries by the inventors.

<First Embodiment>

A configuration of a substrate processing apparatus in accordance with afirst embodiment of the present invention will be described below.

(1) Entire Configuration of Substrate Processing Apparatus

FIG. 1 is a perspective view of a substrate processing apparatus 101 ofthe embodiment. As shown in FIG. 1, the substrate processing apparatus101 in accordance with the embodiment includes a housing 111. In orderto convey a wafer 200, which is a substrate, into/from the housing 111,a cassette 110, which is a wafer carrier (a substrate receiving vessel)configured to receive a plurality of wafers 200, is used. A cassetteloading/unloading port (a substrate-receiving vessel loading/unloadingport, not shown), which is an opening through the cassette 110 isconveyed into/from the housing 111, is installed in the front of thehousing 111. A cassette stage 114 (a substrate-receiving vessel deliveryplatform) is installed inside the cassette loading/unloading port insidethe housing 111. The cassette 110 is placed on the cassette stage 114 bya conveyance apparatus in a factory (not shown), is configured to beunloaded to the outside of the housing 111 from above the cassette stage114.

The cassette 110 is configured to be placed on the cassette stage 114 bythe conveyance apparatus in the factory such that the wafer 200 in thecassette 110 is in a vertical posture and a wafer entrance of thecassette 110 is directed upward. The cassette stage 114 is configuredsuch that the cassette 110 is rotated 90° toward a rear side of thehousing 111 to place the wafer 200 in the cassette 110 in a horizontalposture, and the wafer entrance of the cassette 110 is directed to therear side in the housing 111.

A cassette shelf 105 (a substrate receiving vessel placing shelf) isinstalled at a substantially center portion in the housing 111 in aforward-backward direction. The cassette shelf 105 is configured tostore a plurality of cassettes 110 in multiple rows and multiplecolumns. A transfer shelf 123, in which the cassette 110 conveyed by awafer transfer mechanism 125 (described later) is received, is installedat the cassette shelf 105. In addition, a preliminary cassette shelf 107is configured to be installed over the cassette 114 to store apreliminary cassette 200.

A cassette conveyance apparatus 118 (a substrate receiving vesselconveyance apparatus) is installed between the cassette stage 114 andthe cassette shelf 105. The cassette conveyance apparatus 118 includes acassette elevator 118 a (a substrate receiving vessel elevationmechanism) configured to go up/down with holding the cassette 110, and acassette conveyance mechanism 118 b (a substrate receiving vesselconveyance mechanism), which is a conveyance mechanism that ishorizontally movable while holding the cassette 110. With a continuousoperation of the cassette elevator 118 a and the cassette conveyancemechanism 118 b, the cassette 110 is configured to be conveyed to apredetermined position of the cassette shelf 105 other than the cassettestage 114 and the transfer shelf 123, i.e., between the preliminarycassette shelf 107 and the transfer shelf 123.

A wafer transfer mechanism 125 (a substrate transfer mechanism) isinstalled behind the cassette shelf 105. The wafer transfer mechanism125 includes a wafer transfer apparatus 125 a (a substrate transferapparatus) configured to horizontally rotate or straightly move thewafer 200, and a wafer transfer apparatus elevator 125 b (a substratetransfer apparatus elevation mechanism) configured to raise/lower thewafer transfer apparatus 125 a. In addition, the wafer transferapparatus 125 a includes tweezers 125 c (a substrate holder) configuredto hold the wafer 200 in a horizontal posture. With a continuousoperation of the wafer transfer apparatus 125 a and the wafer transferapparatus elevator 125 b, the wafer 200 is picked up from the cassette110 on the transfer shelf 123 to be charged on a boat 217 (a substrateholder, described later) (wafer charging), or the wafer 200 isdischarged from the boat 217 (wafer discharging), receiving the wafer200 into the cassette 110 on the transfer shelf 123.

The process furnace 202 is installed at a rear upper side of the housing111. An opening is formed at a lower end of the process furnace 202, andconfigured to be opened/closed by a furnace port shutter 147 (a furnaceport opening/closing mechanism). In addition, a configuration of theprocess furnace 202 will be described later.

A transfer chamber 124, which is a space for charging/discharging thewafer 200 from the cassette 110 on the transfer shelf 123 to the boat217 (the substrate holder), is installed under the process furnace 202.A boat elevator 115 (a substrate holder elevation mechanism), which isan elevation mechanism configured to raise/lower the boat 217 toload/unload the boat 217 into/from the process furnace 202, is installedin the transfer chamber 124. An arm 128, which is a connecting tool, isinstalled at an elevation frame of the boat elevator 115. A seal cap219, which is a furnace port cover configured to vertically support theboat 217 and to hermetically close the lower end of the process furnace202 when the boat 217 is raised by the boat elevator 115, is installedon the arm 128 in a horizontal posture.

The boat 217 includes a plurality of holding members, and is configuredto hold a plurality of wafers 200 (for example, about 25 to 125) in amulti-stage in a state where the plurality of wafers 200 areconcentrically aligned in a vertical direction and held in a horizontalposture.

A clean unit 134 a including a supply fan and an anti-vibration filteris installed over the cassette shelf 105. The clean unit 134 a isconfigured to flow clean air of a purified atmosphere into the housing111.

In addition, a clean unit (not shown) including a supply fan forsupplying clean air and an anti-vibration filter is installed at a leftend of the housing 111 opposite to the wafer transfer apparatus elevator125 b and the boat elevator 115. The clean air injected from the cleanunit is suctioned into an exhaust apparatus (not shown) to be exhaustedto the outside of the housing 111, after flowing through the wafertransfer apparatus 125 a and the boat 217.

(2) Operation of Substrate Processing Apparatus

Hereinafter, an operation of the substrate processing apparatus 101 inaccordance with the embodiment will be described.

First, the cassette 110 is placed on the cassette stage 114 such thatthe cassette 110 is loaded through the cassette loading/unloading port(not shown) by the conveyance apparatus in the factory, the wafer is ina vertical posture, and the wafer entrance of the cassette 110 isdirected upward. Then, the cassette 110 is rotated 90° toward a rearside of the housing 111 by the cassette stage 114. As a result, thewafer 200 in the cassette 110 is in a horizontal posture, and the waferentrance of the cassette 110 is directed to a rear side in the housing111.

Next, the cassette 110 is automatically conveyed and delivered to adesignated shelf position of the cassette shelf 105 (except for thetransfer shelf 123) or the preliminary cassette shelf 107 by thecassette conveyance apparatus 118, temporarily stored, and then,transferred to the transfer shelf 123 from the cassette shelf 104 or thepreliminary cassette shelf 107 or directly conveyed to the transfershelf 123.

When the cassette 110 is transferred to the transfer shelf 123, thewafer 200 is picked up from the cassette 110 through the wafer entranceby the tweezers 125 c of the wafer transfer apparatus 125 a to becharged to the boat 217 at a rear side of the transfer chamber 124 by acontinuous operation of the wafer transfer apparatus 125 a and the wafertransfer apparatus elevator 125 b (wafer charging). The wafer transfermechanism 125, which delivered the wafer 200 to the boat 217, returns tothe cassette 110, and then charges the next wafer 200 to the boat 217.

When a predetermined number of wafers 200 are charged to the boat 217,the furnace port shutter 147 closing the lower end of the processfurnace 202 is opened. Next, as the seal cap 219 is raised by the boatelevator 115, the boat 217 holding the group of the wafer 200 is loadedinto the process furnace 202 (boat loading). After the loading,arbitrary processing is performed on the wafer 200 in the processfurnace 202. Such processing will be described later. After theprocessing, the wafer 200 and the cassette 110 are unloaded to theoutside of the housing 111 in reverse sequence of the above sequence.

(3) Configuration of Process Furnace

Next, a configuration of the process furnace 202 in accordance with theembodiment will be generally described with reference to FIGS. 2 and 3.FIG. 2 is a configuration view of the process furnace 202 of thesubstrate processing apparatus 101 shown in FIG. 1, particularly showinga cross-sectional view of a process chamber 201. In addition, FIG. 3 isa cross-sectional view taken along line A-A of the process chamber 201shown in FIG. 2.

(Process Chamber)

The process furnace 202 in accordance with the embodiment is configuredas a batch-type vertical hot-wall process furnace. The process furnace202 includes a reaction tube 203 and a manifold 209. The reaction tube203 is formed of a heat resistant material such as quartz (SiO₂) orsilicon carbide (SiC), and has a cylindrical shape with an upper endclosed and a lower end opened. The manifold 209 is formed of a metalmaterial such as SUS, and has a cylindrical shape with upper and lowerends opened. The reaction tube 203 is vertically supported from thelower end side thereof by the manifold 209. The reaction tube 203 isdisposed concentrically with the manifold 209. An O-ring 220, which is asealing member, is installed between the reaction tube 203 and themanifold 209. A lower end of the manifold 209 is configured to behermetically sealed by the seal cap 219 when the boat elevator 115 israised. An O-ring 220 b, which is a sealing member configured tohermetically seal the inside of the process chamber 201, is installedbetween the lower end of the manifold 209 and the seal cap 219.

The process chamber 201 in which the wafer 200, which is a substrate, isaccommodated is formed in the reaction tube 203 and the manifold 209.The boat 217, which is a substrate holder, is configured to be insertedinto the process chamber 201 from a lower side thereof. Inner diametersof the reaction tube 203 and the manifold 209 are configured to belarger than a maximum outline of the boat 217 to which the wafer 200 ischarged.

The boat 217 is formed of a heat resistant material such as quartz orsilicon carbide, and is configured to hold the plurality of wafers 200in a multi-stage in a state where the plurality of wafers 200 areconcentrically aligned and held in a horizontal posture. In addition, aninsulating member 218 formed of a heat resistant material such as quartzor silicon carbide is installed at a lower part of the boat 217 toreduce heat transfer from a heater 207 (described later) to the seal cap219. Further, the insulating member 218 may be constituted by aplurality of insulating plates formed of a heat resistant material suchas quartz or silicon carbide, and an insulating plate holder configuredto support the plates in a horizontal posture in a multi-stage.

The seal cap 219, which is a furnace port cover configured tohermetically close a lower end opening of the reaction tube 203, isinstalled under the reaction tube 203. The seal cap 219 abuts the lowerend of the reaction tube 203 from a vertical lower side thereof. Theseal cap 219 is formed of a metal material such as SUS and has a discshape. An O-ring 220 b, which is a seal member in contact with the lowerend of the manifold 209, is installed at an upper surface of the sealcap 219.

A rotary mechanism 267 configured to rotate the boat 217 is installed atthe seal cap 219 opposite to the process chamber 201. A rotary shaft 255of the rotary mechanism 267 is connected to the boat 217 through theseal cap 219 to rotate the boat 217, thus rotating the wafer 200. Theseal cap 219 is configured to be vertically raised/lowered by the boatelevator 115, which is an elevation mechanism vertically installedoutside the reaction tube 203 such that the boat 217 can beloaded/unloaded into/from the process chamber 201.

The heater 207, which is a heating unit having a cylindrical shapeconcentric with the reaction tube 203, is installed at an outercircumference of the reaction tube 203. The heater 207 is supported by aheater base (not shown), which is a holding plate, to be installedvertically. In addition, the heater 207 functions as an activationmechanism configured to activate a gas using heat.

A temperature sensor 263, which is a temperature detector, is installedin the reaction tube 203, and a conduction state to the heater 207 isadjusted based on temperature information detected by the temperaturesensor 263 such that a temperature in the process chamber 201 becomes adesired temperature distribution. The temperature sensor 263 has an Lshape similar to nozzles 400 a, 400 b, 400 c and 400 d (describedlater), and is installed along an inner wall of the reaction tube 203.

Mainly, the process chamber 201 is constituted by the reaction tube 203,the manifold 209 and the seal cap 219, and the process furnace 202 isconstituted by the heater 207, the reaction tube 203, the manifold 209and the seal cap 219.

(Nozzle)

A first nozzle 400 a, a second nozzle 400 b, a third nozzle 400 c and afourth nozzle 400 d are installed at a lower portion of the reactiontube 203 in the process chamber 201 to pass through a sidewall of themanifold 209. Each of the nozzles 400 a, 400 b, 400 c and 400 d isconstituted as an L-shaped long nozzle.

Specifically, the nozzles 400 a, 400 b, 400 c and 400 d are installed ina vertical posture in an arc-shaped space between the inner wall of thereaction tube 203 and the wafer 200 from a lower portion to an upperportion of the inner wall of the reaction tube 203 upward in a stackingdirection of the wafers 200. Gas supply holes 401 a, 401 b, 401 c and401 d configured to supply a gas are installed at side surfaces of thenozzles 400 a, 400 b, 400 c and 400 d, respectively. The gas supplyholes 401 a, 401 b, 401 c and 401 d are opened toward a center of thereaction tube 203. The plurality of gas supply holes 401 a, 401 b, 401 cand 401 d are installed from the lower portion to the upper portion ofthe reaction tube 203, each of which has the same opening area at thesame opening pitch.

In addition, as shown in FIG. 3, the nozzles 400 a, 400 b, 400 c and 400d are installed at positions opposite to the temperature sensor 263, forexample, with the wafer 200 interposed therebetween. However, in FIG. 2,in order to show structures of the nozzles 400 a, 400 b, 400 c and 400d, for the sake of convenience, the third nozzle 400 c and the fourthnozzle 400 d and their subsidiary gas supply pipes 410 c and 410 d areshown at a right side of the drawing opposite to the first nozzle 400 aand the second nozzle 400 b.

(First Processing Source Supply Part)

A downstream end of a first processing source gas supply pipe 410 aconfigured to supply a Si-containing gas, which is a first processingsource including silicon (Si) as a first element, for example,hexachlorodisilane (HCD: Si₂Cl₆) gas, is connected to an upstream end (alower portion) of the first nozzle 400 a. An HCD supply source (notshown) configured to supply a liquid source, which is in a liquid phaseat room temperature, a liquid mass flow controller 411 a, which is aflow rate controller (a flow rate control unit), a valve 412 a, which isan opening/closing valve, an evaporator 415 a, and a valve 413 a, whichis an opening/closing valve, are installed at the first processingsource supply pipe 410 a in a sequence from an upstream side thereof.

A downstream end of a carrier gas supply pipe 420 a configured to supplya carrier gas such as nitrogen (N₂) gas supplied into the processchamber 201 with HCD gas generated in the evaporator 415 a is connectedto the evaporator 415 a. A carrier gas supply source (not shown), a massflow controller 421 a, which is a flow rate controller (a flow ratecontrol unit), and a valve 422 a, which is an opening/closing valve, areinstalled at the carrier gas supply pipe 420 a in a sequence from theupstream side thereof. When the valve 412 a is opened and liquid HCDwhose flow rate is controlled by a liquid mass flow controller 411 a issupplied into the evaporator 415 a, the evaporator 415 a is configuredto heat the supplied HCD to generate a vaporized gas of the HCD. Fromthe state in which the HCD gas is generated in the evaporator 415 a, thevalve 422 a is opened, the carrier gas whose flow rate is controlled bythe mass flow controller 421 a is supplied into the evaporator 415 a,and the valve 413 a is opened, such that the HCD gas can be suppliedinto the process chamber 201 with the carrier gas.

A downstream end of a purge gas supply pipe 430 a configured to supply apurge gas such as N₂ gas is connected to the first processing sourcesupply pipe 410 a at a lower side of the valve 413 a. A purge gas supplysource (not shown), a mass flow controller 431 a, which is a flow ratecontroller (a flow rate control unit), and a valve 432 a, which is anopening/closing valve, are installed at the purge gas supply pipe 430 ain a sequence from the upstream side thereof. As the valve 432 a isopened, the purge gas can be supplied into the process chamber 201 fromthe purge gas supply source while controlling a flow rate by the massflow controller 431 a. For example, after completion of supply of theHCD gas, as the purge gas is supplied while exhausting the inside of theprocess chamber 201, the HCD gas remaining in the process chamber 201can be eliminated.

A first processing source supply part configured to supply a firstprocessing source into the process chamber 201 is mainly constituted bythe first processing source supply pipe 410 a, the HCD supply source,the liquid mass flow controller 411 a, the valve 412 a, the evaporator415 a, the valve 413 a, the carrier gas supply pipe 420 a, the carriergas supply source, the mass flow controller 421 a, the valve 422 a, thefirst nozzle 400 a and the gas supply hole 401 a.

(Second Processing Source Supply Part)

A downstream end of a second processing source supply pipe 410 bconfigured to supply a Ti-containing gas as a second processing sourceincluding titanium (Ti) as a second element, for example,tetrachlorotitanium (TiCl₄) gas, is connected to an upstream end (alower portion) of the second nozzle 400 b. A TiCl₄ supply source (notshown) configured to supply TiCl₄ as a liquid source, which is liquid atroom temperature, a liquid mass flow controller 411 b, which is a flowrate controller (a flow rate control unit), a valve 412 b, which is anopening/closing valve, an evaporator 415 b, and a valve 413 b, which isan opening/closing valve, are installed at the second processing sourcesupply pipe 410 b in a sequence from the upstream side thereof.

A downstream end of a carrier gas supply pipe 420 b configured to supplya carrier gas such as N₂ gas supplied into the process chamber 201 withTiCl₄ gas generated in the evaporator 415 b is connected to theevaporator 415 b. A carrier gas supply source (not shown), a mass flowcontroller 421 b, which is a flow rate controller (a flow rate controlunit), and a valve 422 b, which is an opening/closing valve, areinstalled at the carrier gas supply pipe 420 b in sequence from theupstream side thereof. Similar to the case of the first processingsource, as the respective parts are operated, the TiCl₄ gas generated inthe evaporator 415 b can be supplied into the process chamber 201 withthe carrier gas.

A downstream end of a purge gas supply pipe 430 b configured to supply apurge gas such as N₂ gas is connected to the second processing sourcesupply pipe 410 b at a downstream side of the valve 413 b. A purge gassupply source (not shown), a mass flow controller 431 b, which is a flowrate controller (a flow rate control unit), and a valve 432 b, which isan opening/closing valve, are installed at the purge gas supply pipe 430b in a sequence from the upstream side thereof. Similar to the case ofthe purge gas, as the respective parts are operated, the purge gas canbe supplied into the process chamber 201, and thus, the TiCl₄ gasremaining in the process chamber 201 can be eliminated.

A second processing source supply part configured to supply a secondprocessing source into the process chamber 201 is mainly constituted bythe second processing source supply pipe 410 b, the TiCl₄ supply source,the liquid mass flow controller 411 b, the valve 412 b, the evaporator415 b, the valve 413 b, the carrier gas supply pipe 420 b, the carriergas supply source, the mass flow controller 421 b, the valve 422 b, thesecond nozzle 400 b and the gas supply hole 401 b.

(Oxidizing Source Supply Part)

A downstream end of an oxidizing source supply pipe 410 c configured tosupply an oxidizing source such as an oxygen (O) containing gas, forexample, vapor (H₂O gas), is connected to an upstream end (a lowerportion) of the third nozzle 400 c.

A H₂O gas supply source (not shown) configured to supply H₂O gas, a massflow controller 411 c, which is a flow rate controller (a flow ratecontrol unit), and a valve 412 c, which is an opening/closing valve, areinstalled at the oxidizing source supply pipe 410 c in a sequence fromthe upstream side thereof. Meanwhile, when the H₂O gas is supplied,oxygen (O₂) gas and hydrogen (H₂) gas may be supplied into a pyrogenicfurnace to generate H₂O gas.

A downstream end of an inert gas supply pipe 420 c configured to supplyan inert gas such as N₂ gas is connected to a downstream side of thevalve 412 c. An inert gas supply source (not shown), a mass flowcontroller 421 c, which is a flow rate controller (a flow rate controlunit), and a valve 422 c, which is an opening/closing valve, areinstalled at the inert gas supply pipe 420 c in sequence from theupstream side thereof. As the valves 412 c and 422 c are opened, the H₂Owhose gas flow rate is controlled by the mass flow controller 412 c canbe supplied into the process chamber 201 with the inert gas, which is acarrier gas whose flow rate is controlled by the mass flow controller422 c.

In addition, in a state in which the valve 422 c is opened with thevalve 412 c closed and the flow rate is controlled by the mass flowcontroller 421 c, the inert gas is supplied into the process chamber 201as a purge gas so that the H₂O gas, etc., remaining in the processchamber 201 can be eliminated. Further, similar to the case of the firstprocessing source and the second processing source, the purge gas supplypipe configured to supply the purge may be installed separately from theinert gas supply pipe 420 c configured to supply the carrier gas.

The oxidizing source supply part configured to supply the oxidizingsource into the process chamber 201 is mainly constituted by theoxidizing source supply pipe 410 c, the H₂O gas supply source, the massflow controller 411 c, the valve 412 c, the inert gas supply pipe 420 c,the inert gas supply source, the mass flow controller 421 c, the valve422 c, the third nozzle 400 c and the gas supply hole 401 c.

(Catalyst Supply Part)

A downstream end of a catalyst supply pipe 410 d configured to supply acatalyst such as ammonia (NH₃) gas is connected to an upstream end (alower portion) of the fourth nozzle 400 d. An NH₃ gas supply source (notshown) configured to supply NH₃ gas, a mass flow controller 411 d, whichis a flow rate controller (a flow rate control unit), and a valve 412 d,which is an opening/closing valve, are installed at the catalyst supplypipe 410 d in a sequence from the upstream side thereof.

A downstream end of an inert gas supply pipe 420 d configured to supplyan inert gas such as N₂ gas is connected to a downstream side of thevalve 412 d. An inert gas supply source (not shown), a mass flowcontroller 421 d, which is a flow rate controller (a flow rate controlunit), and a valve 422 d, which is an opening/closing valve, areinstalled at the inert gas supply pipe 420 d in a sequence from theupstream side thereof. Similar to the case of the oxidizing source, asthe respective operations are executed, the NH₃ gas can be supplied intothe process chamber 201 with the inert gas, which is a carrier gas.

In addition, as the inert gas is supplied into the process chamber 201as a purge gas, the NH₃ gas remaining in the process chamber 201 can beeliminated. Further, similar to the case of the first processing sourceor the second processing source, the purge gas supply pipe configured tosupply the purge gas may be installed separately from the inert gassupply pipe 420 d configured to supply the carrier gas.

The catalyst supply part configured to the catalyst into the processchamber 201 is mainly constituted by the catalyst supply pipe 410 d, theNH₃ gas supply source, the mass flow controller 411 d, the valve 412 d,the inert gas supply pipe 420 d, the inert gas supply source, the massflow controller 421 d, the valve 422 d, the fourth nozzle 400 d and thegas supply hole 401 d.

(Exhaust Part)

A gas exhaust pipe 231 configured to exhaust an atmosphere in theprocess chamber 201 is installed at the reaction tube 203. A vacuum pump246, which is a vacuum exhaust apparatus, is connected to the gasexhaust pipe 231 via a pressure sensor 245, which is a pressure detector(a pressure detection part) configured to detect a pressure in theprocess chamber 201 and an automatic pressure controller (APC) valve243, which is a pressure regulator (a pressure regulation part), and isconfigured such that the pressure in the process chamber 201 isvacuum-exhausted to a predetermined pressure (a level of vacuum). TheAPC valve 243 is an opening/closing valve capable of opening/closing thevalve to perform vacuum exhaust/vacuum exhaust stoppage of the inside ofthe process chamber 201 and adjusting a valve opening angle to adjustthe pressure.

In addition, as shown in FIG. 3, the gas exhaust pipe 231 is installedat, for example, a lower sidewall of the reaction tube 203 between thefirst nozzle 400 a and the temperature sensor 263. However, in FIG. 2,in order to show structures of the gas exhaust pipe 231, the APC valve243, the vacuum pump 246 and the pressure sensor 245, for the sake ofconvenience, the configuration including the gas exhaust pipe 231 isshown at a right side of the drawing opposite to the first nozzle 400 aand the second nozzle 400 b.

The exhaust part is mainly constituted by the gas exhaust pipe 231, theAPC valve 243, the vacuum pump 246 and the pressure sensor 245.

(Control Unit)

The controller 280, which is a control unit, is connected to the liquidmass flow controllers 411 a, 411 b and 411 c, the mass flow controllers421 a, 431 a, 421 b, 431 b, 421 c, 431 c, 411 d and 421 d, the valves412 a, 413 a, 422 a, 432 a, 412 b, 413 b, 422 b, 432 b, 412 c, 413 c,422 c, 432 c, 412 d and 422 d, the APC valve 243, the pressure sensor245, the vacuum pump 246, the heater 207, the temperature sensor 263,the rotary mechanism 267, the boat elevator 115, and so on. Thecontroller 280 controls the flow rate adjusting operations of variousgases by the liquid mass flow controllers 411 a, 411 b and 411 c and themass flow controllers 421 a, 431 a, 421 b, 431 b, 421 c, 431 c, 411 dand 421 d, the opening/closing operations of the valves 412 a, 413 a,422 a, 432 a, 412 b, 413 b, 422 b, 432 b, 412 c, 413 c, 422 c, 432 c,412 d and 422 d, the pressure regulating operations based on theopening/closing of the APC valve 243 and the pressure sensor 245, thetemperature control operation of the heater 207 based on the temperaturesensor 263, the start/stop of the vacuum pump 246, the rotational speedadjusting operation of the rotary mechanism 267, the elevating operationof the boat elevator 115, and so on.

(4) Substrate Processing Process

Next, the substrate processing process in accordance with the embodimentwill be described. The substrate processing process in accordance withthe embodiment, which is one process of a process of manufacturing asemiconductor device such as a CMOS image sensor, is performed by theprocess furnace 202, and similar to FIG. 10 b, which will be describedin detail, a silicon titanium oxide (SiTiO) film 21 having a highrefractive index and a silicon oxide (SiO) film 20 having a lowrefractive index are sequentially formed on the resist lens 10. Inaddition, the SiO film is a silicon oxide film having an arbitrarycomposition ratio including SiO₂.

A film forming method includes a chemical vapor deposition (CVD) methodin which a plurality of gases containing a plurality of elementsconstituting a film to be formed are simultaneously supplied, and anatomic layer deposition (ALD) method in which a plurality of gasescontaining a plurality of elements constituting a film to be formed arealternately supplied. Then, the silicon oxide (SiO) film, etc., isformed by controlling supply conditions such as a gas supply flow rate,a gas supply time, a plasma power, and so on, upon the gas supply.

In these film forming methods, for example, supply conditions arecontrolled such that a composition ratio of the film becomes N/Si≈1.33,which is a stoichiometric composition, when a titanium nitride (SiN)film is formed, and a composition ratio of the film becomes O/Si≈2,which is a stoichiometric composition, when a silicon oxide (SiO) filmis formed.

In addition, supply conditions may be controlled such that a compositionof a film to be formed becomes another predetermined composition ratiodifferent from a stoichiometric composition. That is, the supplyconditions may be controlled such that at least one element among theplurality of elements constituting the film to be formed exceeds thestoichiometric composition more than another element. As describedabove, the film forming may be performed while controlling a ratio ofthe plurality of elements constituting the film to be formed (thecomposition ratio of the film).

Further, the term “metal film” means a film formed of a conductivematerial containing metal atoms, and includes, in addition to aconductive metal mono-film formed of a metal monomer, a conductive metalnitride film, a conductive metal oxide film, a conductive metaloxynitride film, a conductive metal complex film, a conductive metalalloy film, a conductive metal silicide film, and so on. For example,the titanium nitride layer is a conductive metal nitride film.

Hereinafter, the substrate processing process in accordance with theembodiment will be described in detail with reference to FIGS. 4 and 5.FIG. 4 is a flowchart of the substrate processing process performed bythe process furnace 202. In addition, FIG. 5 is a timing chart showingeach gas supply timing when supply of the respective gases isalternately repeated according to the embodiment. In the followingdescription, operations of the respective parts constituting the processfurnace 202 shown in FIG. 2 are controlled by the controller 280.

<Substrate Loading Process S101>

First, the plurality of wafers 200 on which the resist lenses 10 arepreviously formed are charged to the boat 217 (wafer charging). Then,the boat 217 on which the plurality of wafers 200 are held is raised bythe boat elevator 115 to be loaded into the process chamber 201 (boatloading). In this state, the seal cap 219 seals the lower end of themanifold 209 via the O-ring 220 b. In the substrate loading processS101, the valves 432 a and 432 b of the purge gas supply pipes 430 a and430 b and the valves 422 c and 422 d of the inert gas supply pipes 420 cand 420 d may be opened to continuously supply the purge gas such as N₂gas into the process chamber 201.

<Pressure Reduction Process S102 and Temperature Increase Process S103>

Next, the valves 432 a, 432 b, 422 c and 422 d are closed, and theinside of the process chamber 201 is exhausted by the vacuum pump 246.At this time, as an opening angle of the APC valve 243 is adjusted, theinside of the process chamber 201 is under a predetermined pressure. Inaddition, the temperature in the process chamber 201 is controlled bythe heater 207 such that the wafer 200 arrives at a desired temperature,for example, room temperature to 200° C., more preferably, roomtemperature to 150° C., for example, 100° C. At this time, a conductionstate to the heater 207 is feedback controlled based on temperatureinformation detected by the temperature sensor 263 such that the insideof the process chamber 201 arrives at a desired temperaturedistribution. Then, the boat 217 is rotated by the rotary mechanism 267to initiate rotation of the wafer 200.

<Lower Layer Oxide Film Forming Process S104 a to S106>

Next, processes S104 a to S106 of FIG. 4 are performed to form a SiTiOfilm 21, which is a lower layer oxide film (a high refractive indexoxide film), on the resist lens 10 formed on the wafer 200 (see FIG.10B). The lower layer oxide film forming process S104 a to S106 includesa first cycle process of setting processes S104 a to S104 d as one cycleand performing the cycle a predetermined number of times S104 e, and asecond cycle process of setting processes S105 a to S105 d as one cycleand performing the cycle a predetermined number of times S105 e. Thefirst cycle process S104 a to S104 e and the second cycle process S105 ato S105 e are set as one set, and the set is performed with apredetermined combination a predetermined number of times (S106),forming the SiTiO film 21. In addition, the SiTiO film 21 is a complexoxide film of Si and Ti having an arbitrary composition ratio.Hereinafter, the first cycle process S104 a to S104 e and the secondcycle process S105 a to S105 e will be described in detail.

<First Processing Source and Catalyst Supply Process S104 a>

In the first processing source and catalyst supply process S104 a of thefirst cycle process S104 a to S104 e, HCD gas, which is a firstprocessing source, and NH₃ gas, which is a catalyst, are supplied intothe process chamber 201.

Specifically, first, before initiating supply of the HCD gas, the HCDgas is previously generated in the evaporator 415 a. That is, the valve412 a is opened, and liquid HCD is supplied into the evaporator 415 awhile controlling a flow rate by the liquid mass flow controller 411 a,generating the HCD gas. When the HCD gas is supplied, the valve 422 a isopened, and the carrier gas is supplied into the evaporator 415 a whilecontrolling a flow rate by the mass flow controller 421 a. In addition,the valve 413 a is opened, and the generated HCD gas is supplied intothe process chamber 201 with the carrier gas.

In addition, the valves 412 d and 422 d are opened, and the NH₃ gas issupplied into the process chamber 201 with the inert gas, which is acarrier gas, while controlling flow rates by the mass flow controllers411 d and 421 d, respectively.

When the HCD gas and the NH₃ gas are supplied into the process chamber201, an opening angle of the APC valve 243 is adjusted to bring theinside of the process chamber 201 to a predetermined pressure, forexample, 10 Torr. A flow rate ratio of the HCD gas and the NH₃ gas is aratio of a flow rate (sccm) of the HCD gas/a flow rate (sccm) of the NH₃gas, for example, 0.01 to 100, more preferably 0.05 to 10. A supply timeof the HCD gas and the NH₃ gas is, for example, 1 second to 100 seconds,more preferably, 5 seconds to 30 seconds. When a predetermined timeelapses, the valves 412 a, 413 a, 422 a and 412 d are closed, and supplyof the HCD gas and the NH₃ gas into the process chamber 201 is stopped.In addition, the valve 422 d is kept open.

As described above, the HCD gas and the NH₃ gas supplied into theprocess chamber 201 pass over the wafer 200 to be exhausted through thegas exhaust pipe 231. When the HCD gas passes over the wafer 200, theHCD gas is chemisorbed to a surface of the resist lens 10 on the waferor a surface of a Si-containing layer formed by adsorbing HCD molecule(or decomposed matters thereof) on the resist lens 10, forming theSi-containing layer.

The NH₃ gas accelerates formation of the Si-containing layer bychemosorption of the HCD gas. That is, as shown in FIG. 6A, the NH₃ gas,which is a catalyst, is reacted with an OH-bond of a surface of, forexample, the resist lens 10 or the Si-containing layer, weakening abonding force between O—H. Hydrogen (H), a bonding force of which isweakened, is reacted with chlorine (Cl) of the HCD gas to separatehydrogen chloride (HCl) gas, and HCD molecules (a halide), from which Clis lost, is chemisorbed with the surface of the resist lens 10, etc. TheNH₃ gas weakens the bonding force between O—H because N atoms havinglone electron pairs in the NH₃ molecules function to pull H. Since theNH₃ gas has an acid dissociation constant (hereinafter referred to aspKa), which is an index of a force pulling H, of about 9.2, the forcepulling H is relatively strong.

<Exhaust Process S104 b>

As described above, after a predetermined time has elapsed to stopsupply of the HCD gas and the NH₃ gas, the APC valve 243 is opened toexhaust an atmosphere in the process chamber 201, eliminating theremaining HCD gas, NH₃ gas, decomposed matters after reaction (anexhaust gas), and so on. In addition, in a state in which the valve 422d is opened, the valve 432 a is opened, and the purge gas is suppliedinto the process chamber 201 while controlling a flow rate by the massflow controllers 431 a and 421 d. At this time, the valves 432 b and 422c may be further opened, and the purge gas may be supplied through thepurge gas supply pipe 430 b or the inert gas supply pipe 420 c.Accordingly, the effect of eliminating the remaining gas from the insideof the process chamber 201 can be further improved. After apredetermined time elapses, the valves 432 a and 422 d are closed andthe exhaust process S104 b is terminated.

<Oxidizing Source and Catalyst Supply Process S104 c>

After removing the remaining gas in the process chamber 201, the H₂Ogas, which is an oxidizing source, and the NH₃ gas, which is a catalyst,are supplied into the process chamber 201. That is, the valves 412 c and422 c are opened, and the H₂O gas is supplied into the process chamberwith the inert gas, which is a carrier gas, while controlling flow ratesby the mass flow controllers 411 c and 421 c. In addition, in the samesequence as the first processing source and catalyst supply process S104a, the NH₃ gas is supplied into the process chamber 201 with the inertgas, which is a carrier gas.

When the H₂O gas and the NH₃ gas are supplied into the process chamber201, the pressure in the process chamber 201 is, for example, 10 Torr.In addition, for example, a ratio of a flow rate (sccm) of the H₂O gas/aflow rate (sccm) of the NH₃ gas is 0.01 to 100, more preferably, 0.05 to10. At this time, it is more preferable that mass percent concentrationsof the H₂O gas and the NH₃ gas are substantially equal to each other.The supply time of the gases may be, for example, 1 second to 100seconds, more preferably, 5 seconds to 30 seconds. When a predeterminedtime elapses, the valves 412 c and 412 d are closed, and supply of theH₂O gas and the NH₃ gas into the process chamber 201 is stopped. Inaddition, the valves 422 c and 422 d are kept open.

As described above, the H₂O gas and the NH₃ gas supplied into theprocess chamber 201 pass over the wafer 200 to be exhausted through thegas exhaust pipe 231. When passing over the wafer 200, the H₂O gassurface-reacts with the Si-containing layer, etc., formed on the resistlens 10, and the Si-containing layer, etc., is oxidized to be convertedinto a SiO layer. In addition, the SiO layer is a silicon oxide layerhaving an arbitrary composition ratio including SiO₂.

The NH₃ gas accelerates the surface reaction of the H₂O gas with theSi-containing layer. That is, as shown in FIG. 6B, the NH₃ gas, which isa catalyst, reacts with an O—H bond included in the H₂O gas to weakenthe bonding force between O—H. H, a bonding force of which is weakened,reacts with Cl included in the Si-containing layer on the resist lens 10to separate hydrogen chloride (HCl) gas, and O of the H₂O gas, fromwhich H is lost, is added to Si, from which Cl is separated.

<Exhaust Process S104 d>

After stopping supply of the H₂O gas and the NH₃ gas, the APC valve 243is opened to exhaust the atmosphere in the process chamber 201, and theremaining H₂O gas, NH₃ gas, decomposed matters after reaction (exhaustgas), etc., are eliminated. In addition, the inert gas, which is a purgegas, is supplied into the process chamber 201 while controlling flowrates by the mass flow controllers 421 c and 421 d via the valves 422 cand 422 d in an open state. At this time, another purge gas supply pipemay be used. After a predetermined time elapses, the valves 422 c and422 d are closed to stop the exhaust process S104 d.

<Process of Performing Predetermined Number of Times S104 e>

The processes S104 a to S104 d are set as one cycle and the cycle isperformed a predetermined number of times, forming the SiO layer on theresist lens 10 of the wafer 200 to a predetermined film thickness, forexample, 2.0 Åto 10,000 Å. FIG. 5 shows an example in which the cycle isperformed p times. A horizontal axis of FIG. 5 represents elapsed time,and a vertical axis of FIG. 5 represents a gas supply timing of eachgas. From the above, the first cycle process S104 a to S104 e isterminated.

As described above, in each of the first processing source and catalystsupply process S104 a and the oxidizing source and catalyst supplyprocess S104 c, since the NH₃ gas is used as a catalyst, chemisorptionof the HCD gas can be accelerated even under a low temperature, andsurface reaction of the H₂O gas can also be accelerated. As describedabove, as the SiO layer is formed under a low temperature, thermaldenaturation of the resist lens 20 can be suppressed and occurrence ofbad resist lenses 10 can be reduced.

<Second Processing Source and Catalyst Supply Process S105 a>

In the second processing source and catalyst supply process S105 a ofthe second cycle process S105 a to S105 e, TiCl₄ gas, which is a secondprocessing source, and NH₃ gas, which is a catalyst, are supplied intothe process chamber 201.

Specifically, first, before initiating supply of the TiCl₄ gas, theTiCl₄ gas is previously generated in the evaporator 415 b. That is, thevalve 412 b is opened, and liquid TiCl₄ is supplied into the evaporator415 b to generate the TiCl₄ gas while controlling a flow rate of theliquid mass flow controller 411 b. When the TiCl₄ gas is supplied, thevalve 422 b is opened, and the carrier gas is supplied into theevaporator 415 b while controlling a flow rate by the mass flowcontroller 421 b. In addition, the valve 413 b is opened, and thegenerated TiCl₄ gas is supplied into the process chamber 201 with thecarrier gas. Further, in a sequence similar to the first processingsource and catalyst supply process S104 a, the NH₃ gas is supplied intothe process chamber 201 with the inert gas, which is a carrier gas.

The pressure, supply amount and supply time of the gas, etc., when theTiCl₄ gas and the NH₃ gas are supplied into the process chamber 201 maybe the same as in the first processing source and catalyst supplyprocess S104 a. When a predetermined time elapses, the valves 412 b, 413b, 422 b and 412 d are closed, and supply of the TiCl₄ gas and the NH₃gas into the process chamber 201 is stopped. In addition, the valve 422d is kept open.

Similar to the first processing source and catalyst supply process S104a, chemisorption of the TiCl₄ gas is accelerated by the NH₃ gas, and aTi-containing layer is formed on a surface of the SiO layer, a surfaceof the already formed Ti-containing layer, etc.

<Exhaust Process S105 b>

After stopping supply of the TiCl₄ gas and the NH₃ gas, the APC valve243 is opened to exhaust the atmosphere in the process chamber 201 andthe remaining TiCl₄ gas or NH₃ gas, decomposed matters after reaction(exhaust gas), etc., are eliminated. In addition, the valve 432 isfurther opened in a state in which the valve 422 d is opened, and thepurge gas is supplied into the process chamber 201 while controlling aflow rate by the mass flow controller 431 b and 421 d. At this time,another purge gas supply pipe, etc., may be used. After a predeterminedtime elapses, the valves 432 b and 422 d are closed to stop the exhaustprocess S105 b.

<Oxidizing Source and Catalyst Supply Process S105 c>

In a sequence and processing conditions similar to the oxidizing sourceand catalyst supply process S104 c, the H₂O gas and the NH₃ gas aresupplied into the process chamber 201. The Ti-containing layer, etc., isoxidized by a reaction similar to the oxidizing source and catalystsupply process S104 c to be converted into a TiO layer. In addition, theTiO layer is a titanium oxide layer, which is a metal oxide layer,having an arbitrary composition ratio including TiO₂.

<Exhaust Process S105 d>

In a sequence similar to the exhaust process S104 d, the atmosphere inthe process chamber 201 is exhausted to eliminate the remaining H₂O gas,etc. In addition, the purge gas is supplied into the process chamber201.

<Process S105 e of Performing Predetermined Number of Times>

The processes S105 a to S105 d are set as one cycle and the cycle isperformed a predetermined number of times. The TiO layer is formed onthe SiO layer of the wafer 200 to a predetermined film thickness, forexample, 2.0 Åto 10,000 Å. FIG. 5 shows an example in which the cycle isperformed q times. From the above, the second cycle process S105 a toS105 e is terminated.

As described above, even when the TiO layer is formed using the TiCl₄gas, the NH₃ gas may be used as a catalyst in each of the secondprocessing source and catalyst supply process S105 a and the oxidizingsource and catalyst supply process S105 c, accelerating chemisorption ofthe TiCl₄ gas even under a low temperature and also accelerating surfacereaction of the H₂O gas. As described above, when the TiO layer isformed under a low temperature, thermal denaturation of the resist lens10 can be suppressed to reduce occurrence of a bad resist lens 10.

<Process S106 Performed Predetermined Number of Times>

In the process S106 performed a predetermined number of times, the firstcycle process S104 a to S104 e and the second cycle process S105 a toS105 e are set as one set, and the set is performed with a predeterminedcombination a predetermined number of times (for example, p times and qtimes, respectively), forming the SiTiO film 21 on the resist lens 10 ofthe wafer 200 to a predetermined film thickness, for example, 50 Å to20,000 Å (see FIG. 10B).

Since a refractive index of the TiO layer is 2.2, which is relativelyhigher than 1.45—a refractive index of the SiO—as described above, theSiTiO film 21 formed by depositing the SiO layer and the TiO layer canobtain a high refractive index closer to the resist lens 10 than in theSiO film formed on its own. In addition, the SiTiO film 21 having apredetermined refractive index may be formed by arbitrarily adjusting adeposition ratio of the TiO layer with respect to the SiO layer. Thedeposition ratio may be adjusted by the combination, i.e., the number oftimes each cycle process is performed. For example, when the number oftimes the first cycle process S104 a to S104 e is performed is 3 (p=3)and the number of times of the second cycle process S105 a to S105 e isperformed is 2 (q=2), the SiTiO film 21 having a refractive index of1.55 can be obtained. In addition, when p=3 and q=1, the refractiveindex becomes 1.50. The refractive index of the SiTiO film 21 isselected within a range of more than a refractive index of air to lessthan a refractive index of the resist lens 10.

In addition, in a state in which the arbitrary combination ismaintained, as the first cycle process S104 a to S104 e and the secondcycle process S105 a to S105 e are set as one set and the number oftimes the set is performed is varied, the film thickness of the SiTiOfilm 21 can be controlled in a state in which a predetermined refractiveindex is maintained. Further, the first cycle process S104 a to S104 eand the second cycle process S105 a to S105 e may be performed in anarbitrary sequence, and the lower layer oxide film forming process S104a to S106 may be initiated from an arbitrary process or may beterminated at an arbitrary process. For example, the lower layer oxidefilm forming process S104 a to S106 may be initiated from the secondcycle process S105 a to S105 e and may be terminated at the second cycleprocess S105 a to S105 e.

<Upper Layer Oxide Film Forming Process S107 a to S107 e>

Next, the processes S107 a to S107 d are set as one cycle and the cycleis performed a predetermined number of times S107 e, forming the SiOfilm 20 on the SiTiO film 21 of the wafer 200 as an upper layer oxidefilm (a low refractive index oxide film) (see FIG. 10B). Each process ofthe processes S107 a to S107 d is performed in a sequence and processingconditions similar to each process of the processes S104 a to S104 d.Since these processes are performed a predetermined number of times, theSiO film 20 is formed on the SiTiO film 21 to a predetermined filmthickness, for example, 50 Å to 10,000 Å. At this time, the refractiveindex of the SiO film 20 is within a range of more than the refractiveindex of air to less than the refractive index of the SiTiO film 21.FIG. 5 shows an example in which the cycle is performed r times.

As described above, in this embodiment, the SiO film 20 having arelatively low refractive index is formed on the SiTiO film 21 having arelatively high refractive index to gradually reduce the refractiveindex in a thickness direction from the resist lens 10 to the air.Accordingly, in comparison with the case of forming only the SiO film20, a difference in refractive index between the media can be furtherattenuated to further suppress the reflection.

<Temperature Reduction Process S108 and Normal Pressure ReturningProcess S109>

When the SiTiO film 21 and the SiO film 20 are formed to a desired filmthickness, power supply to the heater 207 is stopped, and the boat 217and the wafer 200 are cooled to a predetermined temperature. Whilereducing the temperature, the valves 432 a, 432 b, 422 c and 422 d arekept open, and supply of the purge gas into the process chamber 201 fromthe purge gas supply source (not shown) is continued. Accordingly, theinside of the process chamber 201 is substituted by the purge gas, andthe pressure in the process chamber 201 returns to a normal pressure.

<Substrate Unloading Process S110>

When the wafer 200 is cooled to a predetermined temperature and theinside of the process chamber 201 returns to a normal pressure, inreverse sequence of the above sequence, the film-formed wafer 200 isunloaded from the process chamber 201. In addition, when the boat 217 isunloaded, the valves 432 a, 432 b, 422 c and 422 d are opened, and thepurge gas may be continuously supplied into the process chamber 201.Therefore, the substrate processing apparatus in accordance with theembodiment is terminated.

(5) Effects According to the Embodiment

According to the embodiment, the following one or more effects areprovided.

(a) According to the embodiment, the SiTiO film 21 and the SiO film 20are formed on the resist lens 20 formed on the wafer 200 in sequence. Atthis time, the refractive index of the SiTiO film 21 is controlledwithin a range of more than the refractive index of air to less than therefractive index of the resist lens 10, and the refractive index of theSiO film 20 is within a range of more than the refractive index of airto less than the refractive index of the SiTiO film 21.

As described above, as the refractive index can be varied when the oxidefilm is formed and the refractive index is gradually reduced in athickness direction from the resist lens 10 to the air, a difference inrefractive index between the media can be attenuated to suppressreflection of the resist lens 10, improving light-collecting efficiency.FIG. 10B shows a shape in which the refractive index is attenuated tosuppress reflection (reflective light 6 a, 6 b and 6 c) of surfaces ofthe respective films.

(b) In addition, according to the embodiment, the SiO film 20 iscombined with the SiTiO film 21 having a relatively high refractiveindex. Accordingly, in comparison with the case in which only the SiOfilm 20 having a relatively low refractive index is formed, since lightcan easily enter the photo diode 30 even when the light enters in a sidedirection, light collection from a wider angle becomes possible.

In a semiconductor device according to reference example, on which onlythe SiO film 20 is formed, as show in FIG. 10A, since the refractiveindex of the SiO film 20 is low, light collection from the wide anglemay become difficult. That is, since refraction of incident light 2 inthe SiO film 20 is shallow (refractive light 7 b), the light is deviatedfrom the photo diode 30 as much as the light enters in a side direction.

However, in this embodiment, since the SiTiO film 21 having a relativelyhigh refractive index is combined with the SiO film 20, as shown in FIG.10B, the incident light 5 can reach the photo diode 30 from a widerangle (refractive light 7 a), improving light collecting efficiency.

(c) In addition, according to the embodiment, the first cycle S104 a toS104 e and the second cycle S105 a to S105 e are set as one set and theset is performed with a predetermined combination a predetermined numberof times (S106), forming the SiTiO film 21. Accordingly, a depositionratio of the TiO layer with respect to the SiO layer can be adjusted toobtain the SiTiO film 21 having a predetermined refractive ratio.

(d) Further, according to the embodiment, since the first cycle S104 ato S104 e and the second cycle S105 a to S105 e are set as one set andthe number of times the set is performed is varied, the film thicknessof the SiTiO film 21 can be controlled. At this time, when thepredetermined combination is maintained, the refractive index of theSiTiO film 21 can be maintained at a predetermined value.

(e) Furthermore, according to the embodiment, the SiTiO film 21 and theSiO film 20 are formed using the NH₃ gas, which is a catalyst. Inaddition, at this time, the heating temperature of the wafer 200 is 200°C. or less, more preferably, 150° C. or less. Using the catalyst, evenunder the low temperature, chemisorption of the HCD gas and the TiCl₄gas can be accelerated and surface reaction of the H₂O gas can also beaccelerated. That is, since only the oxide film such as the SiTiO film21 and the SiO film 20 are mainly formed, the film can be formed usingthe catalyst under the low temperature. Accordingly, thermaldenaturation of the resist lens 10 can be suppressed and occurrence of abad resist lens 10 can be reduced, improving properties thereof.

(f) Further, according to the embodiment, the SiTiO film 21 and the SiOfilm 20 are continuously formed in the same process chamber 201.Accordingly, efforts such as conveyance of the wafer 200 to anotherprocess furnace in the middle of the process can be omitted. Inaddition, since no wafer 200 is exposed to the air in the middle of theprocess, an oxide film of a better quality can be formed.

Furthermore, in this embodiment, while the example in which the NH₃ gasis used as a catalyst is described, the catalyst is not limited toammonia but may be another material such as pyridine.

<Second Embodiment>

Hereinafter, a substrate processing process in accordance with a secondembodiment will be described. Unlike the embodiment in which therefractive index is gradually varied in two steps, in the substrateprocessing process in accordance with the embodiment, a SiTiO film isformed such that a refractive index is gradually reduced in a thicknessdirection from a surface thereof in contact with a resist lens 10 to anopposite surface in contact with air, not forming a SiO film 20. Inaddition, in this embodiment, an example in which pyridine (C₅H₅N) gasis used as a catalyst will be described.

(1) Substrate Processing Process

Hereinafter, the substrate processing process in accordance with theembodiment will be described in detail with reference to FIGS. 7 and 8in detail. The substrate processing process in accordance with theembodiment is also performed using the process furnace 202 of FIGS. 2and 3, and operation of the respective parts is controlled by thecontroller 280. However, since the pyridine is in a liquid phase at roomtemperature, an apparatus of the embodiment includes a catalyst supplypipe 410 d, an evaporator (not shown), and so on.

<Substrate Loading Process S201 to Temperature Increase Process S203>

A substrate loading process S201, a pressure reduction process S202 anda temperature increase process S203 shown in FIG. 7 are performed in thesame sequence as the corresponding processes S101 to S103 of the aboveembodiment.

<Deposition Oxide Film Forming Process S204 a to S206>

Next, processes S204 a to S206 of FIG. 7 are performed to form a SiTiOfilm, which is a deposition oxide film, on a resist lens 10 formed onthe wafer 200. In the deposition oxide film forming process S204 a toS206, a first cycle process S204 a to S204 e and a second cycle processS205 a to S205 e are set as one set and the set is performed with apredetermined combination a predetermined number of times (S206),forming the SiTiO film.

<First Cycle Process S204 a to S204 e>

The first cycle process S204 a to S204 e is performed in a sequence andprocessing conditions similar to the first cycle process S104 a to S104e in accordance with the embodiment. At this time, pyridine gas is usedas a catalyst. Similar to the NH₃ gas, the pyridine gas functions topull H (pKa=5.7) because an N atom of a pyridine molecule has a loneelectron pair. Accordingly, as shown in FIGS. 9A and 9B, a bonding forceof a surface of the resist lens 10 or the Si-containing layer or an O—Hbond in the H₂O gas is weakened, and thus, chemisorption of the HCD gasis accelerated and surface reaction of the H₂O gas is also accelerated.

Accordingly, the SiO layer is formed on the resist lens 10 of the wafer200 to a predetermined film thickness, for example, 2.0 Å to 1,000 Å.FIG. 8 shows an example in which the cycle is performed m times.

<Second Cycle Process S205 a to S205 e>

The second cycle process S205 a to S205 e is performed in a sequence andprocessing conditions similar to the second cycle process S105 a to S105e in accordance with the embodiment. The pyridine gas is used as acatalyst. Accordingly, the TiO layer is formed on the SiO layer of thewafer 200 to a predetermined film thickness, for example, 2.0 Å to 1,000Å. FIG. 8 shows an example in which the cycle is performed n times.

<Process S206 of Performing Predetermined Number of Times>

In the process S206 performed a predetermined number of times, the firstcycle process S204 a to S204 e and the second cycle process S205 a toS205 e are set as one set and the set is performed with a predeterminedcombination (for example, m times and n times, respectively) apredetermined number of times, forming the SiTiO film on the resist lens10 of the wafer 200 to a predetermined film thickness, for example, 2.0Å to 2,000 Å.

Here, in this embodiment, as the deposition ratio of the TiO layer withrespect to the SiO layer is gradually reduced, the SiTiO film is formedsuch that the refractive index is gradually reduced in a thicknessdirection from a surface thereof in contact with the resist lens 10 toan opposite surface in contact with air. Specifically, as the number oftimes the second cycle process S205 a to S205 e is performed withrespect to the number of times the first cycle process S204 a to S204 eis performed, i.e., a value of n with respect to a value of m, isgradually reduced, the first cycle process S204 a to S204 e and thesecond cycle process S205 a to S205 e are set as one set and the set isperformed a predetermined number of times. At this time, the refractiveindex of the SiTiO film is varied within a range of a refractive indexof air to less than a refractive index of the resist lens 10.

In addition, a performing sequence of the first cycle process S204 a toS204 e and the second cycle process S205 a to S205 e is arbitrary. Forexample, the deposition oxide film forming process S204 a to S206 may beinitiated from the second cycle process S205 a to S205 e and may beterminated at the first cycle process S204 a to S204 e.

As described above, in this embodiment, the refractive index may begradually reduced in a thickness direction from the resist lens 10 tothe air and a difference in refractive index between the media may beattenuated, suppressing reflection of the resist lens 10.

<Temperature Reduction Process S208 to Substrate Unloading Process S210>

A temperature reduction process S208, a normal pressure returningprocess S209 and a substrate unloading process S210 are performed in asequence similar to the corresponding processes S108 to S110 of theembodiment. From the above, the substrate processing process inaccordance with the embodiment is terminated.

(2) Effects According to the Embodiment

The embodiment has the same effects as the above embodiment.

(a) In addition, according to the embodiment, the SiTiO film is formedsuch that the refractive index is gradually reduced in the thicknessdirection from the surface in contact with the resist lens 10 to theopposite surface in contact with the air. Accordingly, the difference inrefractive index between the media can be further attenuated to suppressreflection of the resist lens 10.

(b) Further, according to the embodiment, the SiTiO film is formed usingthe pyridine, which is a catalyst. Accordingly, particles are reduced.

As described above, when the NH₃ gas is used as a catalyst, as the NH₃gas and the HCD gas are simultaneously supplied, a reaction between theNH₃ gas and the HCD gas partially occurs so that NH₄Cl is generated as abyproduct, generating particles (see FIG. 6A).

However, in this embodiment, since the pyridine (pKa) gas having asmaller acid dissociation constant pKa than the NH₃ gas and lowreactivity with a group 17 element such as Cl is used as a catalyst,generation of byproducts can be suppressed and particles can be reduced.

<Third Embodiment>

Hereinafter, a substrate processing process in accordance with a thirdembodiment of the present invention will be described below. Thesubstrate processing process in accordance with the embodiment isdistinguished from the above embodiment in that plasma is used insteadof the catalyst to activate the H₂O gas, which is an oxidizing source,improving reactivity.

In the substrate processing process in accordance with the embodiment,in addition to the configuration shown in FIGS. 2 and 3, a processfurnace having a mechanism configured to generate plasma is used. Themechanism mainly includes a buffer chamber, which is a gas distributionspace, installed at an inner wall of the reaction tube 203, a pair ofrod-shaped electrodes installed in the buffer chamber, and a radiofrequency power source connected to the rod-shaped electrodes via anadapter, none of which are shown. The H₂O gas, which is an oxidizingsource, is supplied into the buffer chamber through a third nozzle 400 cdisposed in the buffer chamber and connected to a downstream end of theoxidizing source supply pipe 410 c, and a high frequency power isapplied to the rod-shaped electrodes from the high frequency powersource via the adapter, so that the H₂O gas in a plasma state issupplied into the process chamber 201.

The substrate processing process in accordance with the embodiment isperformed using the process furnace including the configuration asfollows. That is, in the process corresponding to the first processingsource and catalyst supply process S104 a, S107 a and S204 a or thesecond processing source and catalyst supply process S105 a and S205 ain accordance with the embodiment, chemisorption of each source isaccelerated by the catalyst similar to the above embodiment, withoutconverting the first processing source or the second material into aplasma state. In addition, in the oxidizing supply process performed inresponse to each of the source and catalyst supply processes, the H₂Ogas in a plasma state is supplied into the process chamber 201 toaccelerate surface reaction by the H₂O gas, without supplying thecatalyst.

As described above, in this embodiment, the H₂O gas in a plasma statemay be supplied into the process chamber 201 to accelerate surfacereaction by the H₂O gas under a low temperature, even when the catalystis not used.

<Other Embodiments>

Hereinabove, although embodiments of the present invention have beenspecifically described, the present invention is not limited thereto butvarious modifications may be made without departing from the teaching ofthe present invention.

For example, in the embodiments, while the photo resist is used as alens material, in addition to a photosensitive resin such as the photoresist, a resin having plasticity or curability with respect to heat orlight may be used, specifically, acryls, phenols, styrenes, etc. Arefractive index of the acryls is 1.5. These resins may be transparentresins through which light having a predetermined wavelength such asvisible light passes. In addition, for example, an inorganic materialsuch as glass or quartz (SiO₂) may be used as a lens material.

Further, in the embodiment, while supply of the oxidizing source andsupply of the first processing source or the second processing sourceare alternately performed, when a complex oxide film is formed, theoxidizing source may be supplied at predetermined intervals duringalternate supplies of the first processing source and the secondprocessing source a predetermined number of times.

Furthermore, in addition to the HCD gas, silicon-based chloride gasessuch as dichlorosilane (DCS: SiH₂Cl₂) gas, trichlorosilane (SiHCl₃) gas,tetrachlorosilane (SiCl₄) gas, or octachlorotrisilane (Si₃Cl₈) gas,fluoride gases, boromide gases, and iodide gases may be used as theSi-containing gas, which is a first element. In addition, the firstelement may be an element other than Si, or may include a plurality ofelements.

Further, in addition to TiCl₄ gas, various titanium-based chloride,fluoride, boromide and iodide gases may be used as a Ti-containing gas,which is a second element. Furthermore, in addition to Ti, hafnium (Hf),zirconium (Zr), etc., may be used as the second element as long as thepredetermined refractive index can be obtained when a complex oxide filmis formed in combination with the first element such as Si. For example,refractive indices of a HfO layer and a ZrO layer are 2.3 and 2.2,respectively. The second element may include a plurality of elements.

In addition, in addition to the H₂O gas, hydrogen peroxide (H₂O₂) gas, amixed gas of hydrogen (H₂) gas and ozone (O₃) gas, mixed gas plasma ofhydrogen (H₂) gas and oxygen (O₂) gas, etc., may be used as anO-containing gas, which is an oxidizing source. When the catalyst isused as in the embodiment, the gases may be used as the oxidizing sourceas long as the gases containing elements with differentelectro-negativities among molecules have electrical deviation. The O₂gas or O₃ gas with no electrical deviation may be used when the plasmais used as in the third embodiment.

Further, in addition to the NH₃ gas or the pyridine gas, a gas having arelatively high pKa such as trimethylamine [N(CH₃)₃, pKa=9.8] gas,methylamine [H₂N(CH₃), pKa=10.6] gas or triethylamine [N(C₂H₅)₃,pKa=10.7] gas, or a gas having a relatively low pKa similar to thepyridine gas, such as heterocycle to which N is bonded, for example,aminopyridine (C₅H₄N—NH₂, pKa=6.9), picoline [C₅H₄N(CH₃), pKa=6.1],piperazine [C₄H₁₀N₂, pKa=5.7], lutidine [C₅H₃N(CH₃)₂, pKa=7.0], etc.,may be used as the catalyst.

<Preferred Aspects of the Invention>

Hereinafter, preferred aspects of the present invention will beadditionally stated.

An aspect of the present invention provides a method of manufacturing asemiconductor device, including:

(a) forming a lower layer oxide film on a lens formed on a substrateusing a first processing source containing a first element, a secondprocessing source containing a second element, an oxidizing source and acatalyst, the lower layer oxide film having a refractive index greaterthan that of air and less than that of the lens; and

(b) forming an upper layer oxide film on the lower layer oxide filmusing the first processing source, the oxidizing source and thecatalyst, the upper layer oxide film having a refractive index greaterthan that of the air and less than that of the lower layer oxide film.

Preferably, at least one of the process (a) and the process (b) mayinclude heating the substrate to a temperature ranging from roomtemperature to 200° C.

More preferably, at least one of the process (a) and the process (b) mayinclude heating the substrate to a temperature ranging from roomtemperature to 150° C.

Preferably, the first element may contain at least silicon, and thesecond element may contain one of at least titanium, hafnium andzirconium.

Preferably, the lens may include a transparent resin as a majormaterial.

Preferably, the process (a) may include:

(a-1) performing one or more times a first cycle including supplying thefirst processing source and the catalyst into a process chamberaccommodating the substrate; exhausting the process chamber; supplyingthe oxidizing source and the catalyst into the process chamber; andexhausting the process chamber;

(a-2) performing one or more times a second cycle including supplyingthe second processing source and the catalyst into the process chamberaccommodating the substrate; exhausting the process chamber; supplyingthe oxidizing source and the catalyst into the process chamber; andexhausting the process chamber; and

(a-3) performing a combination of the steps (a-1) and (a-2), and

the process (b) may include: performing one or more times a third cycleincluding supplying the first processing source and the catalyst intothe process chamber accommodating the substrate; exhausting the processchamber; supplying the oxidizing source and the catalyst into theprocess chamber; and exhausting the process chamber.

Another aspect of the present invention provides a semiconductor deviceincluding: a lens; a lower layer oxide film disposed on the lens, thelower layer oxide film having a refractive index greater than that ofair and less than that of the lens and being formed using a firstprocessing source containing a first element, a second processing sourcecontaining a second element, an oxidizing source and a catalyst; and anupper layer oxide film disposed on the lower layer oxide film, the upperlayer oxide film having a refractive index greater than that of the airand less than that of the lower layer oxide film and being formed usingthe first processing source, the oxidizing source and the catalyst.

Still another aspect of the present invention provides a substrateprocessing apparatus including: a process chamber configured toaccommodate a substrate, the substrate having a lens disposed thereon;

a heating part configured to heat the substrate;

a first processing source supply part configured to supply a firstprocessing source containing a first element into the process chamber;

a second processing source supply part configured to supply a secondprocessing source containing a second element into the process chamber;

an oxidizing source supply part configured to supply an oxidizing sourceinto the process chamber;

a catalyst supply part configured to supply a catalyst into the processchamber;

an exhaust part configured to exhaust an atmosphere in the processchamber; and

a control unit configured to control the heating part, the firstprocessing source supply part, the second processing source supply part,the oxidizing source supply part, the catalyst supply part and theexhaust part to form a lower layer oxide film on the lens using thefirst processing source, the second processing source, the oxidizingsource and the catalyst, the lower layer oxide film having a refractiveindex greater than that of air and less than that of the lens, and toform an upper layer oxide film on the lower layer oxide film using thefirst processing source, the oxidizing source and the catalyst, theupper layer oxide film having a refractive index greater than that ofthe air and less than that of the lower layer oxide film.

Yet another aspect of the present invention provides a method ofmanufacturing a semiconductor device, including: forming a depositionoxide layer on a lens formed on a substrate using a first processingsource containing a first element, a second processing source containinga second element, an oxidizing source and a catalyst, the depositionoxide layer having a refractive index equal to or greater than that ofair and equal to or less than of the lens,

wherein, in the forming the deposition oxide layer, the deposition oxidelayer is formed such that the refractive index in the deposition oxidelayer is gradually reduced from a surface thereof in contact with thelens to a surface opposite to the lens and in contact with the air.

Preferably, the forming the deposition oxide layer may include: (a)performing m times a first cycle including supplying the firstprocessing source and the catalyst into the process chamberaccommodating the substrate, exhausting the atmosphere in the processchamber, supplying the oxidizing source and the catalyst into theprocess chamber, and exhausting the atmosphere in the process chamber;(b) performing n times a second cycle including supplying the secondprocessing source and the catalyst into the process chamberaccommodating the substrate, exhausting the atmosphere in the processchamber, supplying the oxidizing source and the catalyst into theprocess chamber, and exhausting the atmosphere in the process chamber;and (c) performing the steps (a) and (b) with a combination apredetermined number of times, and

the deposition oxide layer is formed such that the refractive index inthe deposition oxide layer is gradually reduced from a surface thereofin contact with the lens to a surface opposite to the lens and incontact with the air by gradually reducing a value of n with respect toa value of m.

Yet another embodiment of the present invention provides a semiconductordevice including: a lens; and a deposition oxide film formed on the lensusing a first processing source containing a first element, a secondprocessing source containing a second element, an oxidizing source and acatalyst, wherein the deposition oxide film has a refractive index equalto or greater than that of air and equal to or less than that of thelens, and is configured such that the refractive index in the depositionoxide film is gradually reduced from a surface thereof in contact withthe lens to a surface opposite to the lens and in contact with the air.

Yet another aspect of the present invention provides a substrateprocessing apparatus including: a process chamber configured toaccommodate a substrate, the substrate having a lens disposed thereon; aheating part configured to heat the substrate; a first processing sourcesupply part configured to supply a first processing source containing afirst element into the process chamber; a second processing sourcesupply part configured to supply a second processing source containing asecond element into the process chamber; an oxidizing source supply partconfigured to supply an oxidizing source into the process chamber; acatalyst supply part configured to supply a catalyst into the processchamber; an exhaust part configured to exhaust an atmosphere in theprocess chamber; and a control unit configured to control the heatingpart, the first processing source supply part, the second processingsource supply part, the oxidizing source supply part, the catalystsupply part, and the exhaust part to form a deposition oxide film havinga refractive index equal to or greater than that of air and equal to orless than that of the lens on the lens using the first processingsource, the second processing source, the oxidizing source and thecatalyst, wherein the control unit controls the heating part, the firstprocessing source supply part, the second processing source supply part,the oxidizing source supply part, the catalyst supply part, and theexhaust part such that the refractive index in the deposition oxide filmis gradually reduced from a surface thereof in contact with the lens toa surface opposite to the lens and in contact with the air.

Yet another aspect of the present invention provides a method ofmanufacturing a semiconductor device, including: forming a lower layeroxide film on a lens formed on a substrate using a first processingsource containing a first element, a second processing source containinga second element and an oxidizing source in a plasma state, the a lowerlayer oxide film having a refractive index greater than that of air andless than of a lens; and

forming an upper layer oxide film on the lower layer oxide film usingthe first processing source and the oxidizing source in a plasma state,the upper layer oxide film having a refractive index greater than thatof the air and less than that of the lens.

Yet another aspect of the present invention provides a method ofmanufacturing a semiconductor device, including: forming a depositionoxide film on a lens formed on a substrate using a first processingsource containing a first element, a second processing source containinga second element, and an oxidizing source in a plasma state, thedeposition oxide film having a refractive index equal to or greater thanthat of air and equal to or less than of the lens,

wherein, in the forming the deposition oxide film, the deposition oxidefilm is formed such that the refractive index in the deposition oxidefilm is gradually reduced from a surface thereof in contact with thelens to a surface opposite to the lens and in contact with the air.

Yet another aspect of the present invention provides a semiconductordevice including: a lens; and an oxide film disposed on the lens, theoxide film having a refractive index equal to or greater than that ofair and equal to or less than that of the lens,

wherein the oxide film is formed by depositing a silicon oxide layer;and a metal oxide layer containing one of at least titanium, hafnium andzirconium and having a refractive index greater than that of the siliconoxide layer.

Preferably, the oxide film may be configured such that the refractiveindex of the oxide film can be controlled by controlling a depositionratio between the silicon oxide layer and the metal oxide layer.

Preferably, the oxide film may be configured such that the refractiveindex of the oxide film is gradually increased or decreased by graduallyincreasing or decreasing a deposition ratio of the metal oxide layerwith respect to the silicon oxide layer.

Preferably, the oxide film may be formed at a temperature of 100° C. orless.

Preferably, the lens may be a lens for a CMOS image sensor installedover a light receiving element.

What is claimed is:
 1. A method of manufacturing a semiconductor device,comprising forming a laminated film wherein a silicon-containing oxidefilm and a metal-containing oxide film are alternately stacked on asubstrate by alternately performing, a predetermined number of times,(a) performing a first cycle a predetermined number of times, the firstcycle comprising: supplying a silicon-containing source to thesubstrate; supplying an oxidizing source to the substrate; and supplyinga catalyst to the substrate, or the first cycle comprising: supplying asilicon-containing source to the substrate; and supplying an oxidizingsource in a plasma state to the substrate, to form thesilicon-containing oxide film; and (b) performing a second cycle apredetermined number of times, the second cycle comprising: supplying ametal-containing source to the substrate; supplying an oxidizing sourceto the substrate; and supplying a catalyst to the substrate, or thesecond cycle comprising: supplying a metal-containing source to thesubstrate; and supplying an oxidizing source in a plasma state to thesubstrate, to form the metal-containing oxide film.
 2. The methodaccording to claim 1, wherein the (a) and the (b) are alternatelyperformed in forming the laminated film to gradually decrease a stackingratio of the metal-containing oxide film with respect to thesilicon-containing oxide film.
 3. The method according to claim 1,wherein the silicon-containing source comprises at least one selectedfrom a group consisting of chloride, fluoride, bromide, and iodide. 4.The method according to claim 1, wherein the silicon-containing sourcecomprises at least one selected from a group consisting ofhexachlorodisilane, dichlorosilane, trichlorosilane, tetrachlorosilane,and octachlorotrisilane.
 5. The method according to claim 1, wherein themetal-containing source comprises at least one selected from a groupconsisting of chloride, fluoride, bromide, and iodide.
 6. The methodaccording to claim 1, wherein the metal comprises at least one selectedfrom a group consisting of titanium, hafnium, and zirconium.
 7. Themethod according to claim 1, wherein the oxidizing source comprises atleast one selected from a group consisting of H₂O, H₂O₂, a mixed gas ofH₂ and O₃ and a mixed gas of H₂ and O₂.
 8. The method according to claim1, wherein the catalyst comprises at least one selected from a groupconsisting of ammonia, pyridine, trimethylamine, methylamine,triethylamine, aminopyridine, picoline, piperazine and lutidine.
 9. Amethod of manufacturing a semiconductor device, comprising: (a) forminga laminated film wherein a silicon-containing oxide film and ametal-containing oxide film are alternately stacked on a substrate byalternately performing, a predetermined number of times, (a-1)performing a first cycle a predetermined number of times, the firstcycle comprising: supplying a silicon-containing source to thesubstrate; supplying an oxidizing source to the substrate; and supplyinga catalyst to the substrate, or the first cycle comprising: supplying asilicon-containing source to the substrate; and supplying an oxidizingsource in a plasma state to the substrate, to form thesilicon-containing oxide film; and (a-2) performing a second cycle apredetermined number of times, the second cycle comprising: supplying ametal-containing source to the substrate; supplying an oxidizing sourceto the substrate; and supplying a catalyst to the substrate, or thesecond cycle comprising: supplying a metal-containing source to thesubstrate; and supplying an oxidizing source in a plasma state to thesubstrate, to form the metal-containing oxide film; and (b) forming asilicon-containing oxide film on the laminated film by performing athird cycle a predetermined number of times, the third cycle comprising:supplying a silicon-containing source to the substrate; supplying anoxidizing source to the substrate; and supplying a catalyst to thesubstrate, or the third cycle comprising: supplying a silicon-containingsource to the substrate; and supplying an oxidizing source in a plasmastate to the substrate.
 10. A substrate processing apparatus including:a process chamber configured to accommodate a substrate; asilicon-containing source supply part configured to supply asilicon-containing source into the process chamber; a metal-containingsource supply part configured to supply a metal-containing source intothe process chamber; an oxidizing source supply part configured tosupply an oxidizing source into the process chamber; a catalyst supplypart configured to supply a catalyst into the process chamber or aplasma generating mechanism configured to generate plasma and obtain anoxidizing source in a plasma state; and a control unit configured tocontrol the silicon-containing source supply part, the metal-containingsource supply part, the oxidizing source supply part, and catalystsupply part or the plasma generating mechanism to form a laminated filmwherein a silicon-containing oxide film and a metal-containing oxidefilm are alternately stacked on the substrate by alternately performing,a predetermined number of times, (a) performing a first cycle apredetermined number of times, the first cycle comprising: supplying thesilicon-containing source to the substrate; supplying the oxidizingsource to the substrate; and supplying the catalyst to the substrate, orthe first cycle comprising: supplying the silicon-containing source tothe substrate; and supplying the oxidizing source in a plasma state tothe substrate, to form the silicon-containing oxide film; and (b)performing a second cycle a predetermined number of times, the secondcycle comprising: supplying the metal-containing source to thesubstrate; supplying the oxidizing source to the substrate; andsupplying the catalyst to the substrate, or the second cycle comprising:supplying the metal-containing source to the substrate; and supplyingthe oxidizing source in a plasma state to the substrate, to form themetal-containing oxide film.